Readily Deinkable Toners

ABSTRACT

Broadly the invention provides for a deinkable toner composition, an image made with the deinkable toner, and a method for making the toner including a coloring agent; a thermoplastic polymer; and a protein. In another embodiment the toner includes a coloring agent and a thermoplastic polymer where the protein has been incorporated into the polymer itself. In typical embodiments the protein is derived from soybeans but may be from other plant or animal sources. Typically the toner has a positive triboelectric charge of between about 10 to about 40 microCoulomb/g, or a negative triboelectric charge of between about 10 to about 40 microCoulomb/g.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a divisional of application Ser. No. 10/546,744,filed on Jul. 18, 2006, which claims priority to and the benefits ofPCT/US2004/006023, filed on Feb. 27, 2004, which claims priority to andthe benefits of U.S. Provisional Application Ser. No. 60/450,979 filedFeb. 27, 2003; the disclosures of which are hereby incorporated byreference as if completely rewritten herein.

FIELD OF THE INVENTION

The present invention provides plant or animal based (e.g. soy-based)toners for use in office copiers, laser printers, and the like. Theinvention includes resin and toner compositions based on plant or animaloils and/or protein components.

BACKGROUND OF THE INVENTION

Briefly, there is a need to impart inherent “ready deinkabilty” featureto toners used in office copiers and laser printers. Current toners arenot formulated with this feature, so in the manufacture of secondaryfibers from office waste paper a considerable challenge is posed inremoving toners from the printed surface. With a readily deinkable tonerthat has all the required toning and printing attributes similar tocurrent toners, it should be possible to manufacture higher qualitysecondary fiber by conventional chemical deinking or emerging enzymaticdeinking processes. Conventional toners are based on synthetic resinssuch as styrene acrylates, polyesters, polyamides, etc that aretypically difficult to deink. Resins incorporating soybean derivativesincluding derivatives of the oils and/or proteins can have good toningand printing features like the current synthetic resin-based toners withsignificantly improved deinking features. Chemical structure andcompositions of resins derived from soybean-based materials can be mademore sensitive to attack by mild chemical deinking agents or enzymes.Toner work by others has shown that it is possible to make functionaltoners from soy dimer acids. However, their deinking features weremarginal in a typical chemical deinking system and very poor inenzymatic systems.

BRIEF DESCRIPTION OF THE INVENTION

Broadly the invention provides for toner that has improved propertiessuch as ready deinking characteristics. The toner is typically used inelectrostatic type copying and printing machines.

A first embodiment of the invention provides for a toner including acoloring agent; a thermoplastic polymer; and a protein. Typically theprotein is derived from animal or plant sources. Typically the tonercomprises particles having a mean particle size range of less than about100 micrometer and more preferably a mean particle size range of lessthan about 25 micrometer, and most preferably a mean particle size rangeof less than about 20 micrometer. Typically excipients selected from thegroup consisting of charge control agents, flow control agents,lubricants, anticaking agents, and mixtures thereof are used. In sometypical embodiments the toner has a positive triboelectric charge ofbetween about 10 to about 40 microCoulomb/g and more preferably apositive triboelectric charge of between about 10 to about 20microCoulomb/g. In other typical embodiments, the toner has a negativetriboelectric charge of between about 10 to about 40 microCoulomb/g andmore preferably a negative triboelectric charge of between about 10 toabout 20 microCoulomb/g. Some typical embodiments provide for a tonerhaving a polymer glass transition temperature of between about 55° C. toabout 70° C. In yet other typical embodiments the toner includesmagnetic materials.

In broad embodiments of the invention the toner is used with printingand copying paper, in the graphic arts, and in textile printing.

In yet further embodiments of the invention, a method is provided formaking a deinkable toner by the step of compounding a coloring agent; athermoplastic polymer; and a protein. Typically the compounded deinkabletoner is micronized and if needed classified for appropriate particlesize distribution according to the application.

A yet further embodiment of the invention provides for an image preparedwith a deinkable toner composition including a coloring agent; athermoplastic polymer; and a protein. Typically the image density isfrom about 1.0 to about 1.3.

A further embodiment of the invention provides for a deinkable tonerincluding a coloring agent; a thermoplastic polymer; and a protein.Typically the protein is derived from a soya bean.

A yet further embodiment of the invention includes a polyamide from thereaction product of a dimer acid; a diamine; a dibasic amino acid; andan aliphatic acid.

An additional embodiment of the invention includes a polyamide made bythe reaction product of a dimer acid; a diamine; a protein derivative;and an aliphatic acid.

BRIEF DESCRIPTION OF THE DRAWING

The FIGURE is a graph showing the triboelectric charge on the Y axis inmicroCoulomb/gram versus the level of silica additive TG811 in % (byweight) on the X axis.

DETAILED DESCRIPTION OF THE INVENTION AND BEST MODE

The present invention provides soy-based toners for use in officecopiers and laser printers. The examples provide for resin and tonercompositions based on soybean oil and/or protein components that weresynthesized and characterized establish ready deinkability. Selection ofresin composition was based on various considerations such as glasstransition temperature (Tg), mechanical and rheological properties andpropensity to attack by deinking chemicals and enzymatic agents. Resinswere characterized by melt rheology using a Rheometer, melting and Tg byDSC (Differential Scanning Calorimeter) and other relevant molecular andphysical parameters. Formulates of 100-200 gram quantities of about 4-6typical toner compositions using carbon black and flow additive usingthe resins. The toners were tested for particle size and distribution,triboelectric charge density, hand toning, melt rheology, and Tg. Copiertests were made to show printability and image quality of toners

Subsequently further resin synthesis and toner formulations were made toprepare sufficient quantity of resin to formulate 300-400 grams of oneto two toner compositions for more extensive testing and evaluation.Control toners were tested to establish base line performance of currentproducts. The toners were tested in a commercial copier for a sufficientlength of time to generate reasonable quantity of printed paper neededfor deinking tests. Chemical deinking tests were performed to establishready deinking features of toners prepared according to the invention.

Resin Synthesis

Soy-based dimer acid was chosen as one component for a moreenvironmentally sound electrostatic toner based on some results reportedby previous investigators. The dimer acid contains two carboxylic acidfunctionalities (see Formula 1) that can be reacted with diamines toproduce polyamide bonds. Polyamide bonds are known to be susceptible tohydrolysis. Those based on a natural material, such as soybean oil, maybe liable to attack via enzymatic means. Either of these methods ofdisintegration, hydrolysis or enzymatic degradation, should promote theremoval of the resin from the paper surface, giving the toner gooddeinking properties. Other researchers reported that adding amino acids,such as tyrosine or glutamic acid, into the resin composition encouragesswelling of the resin upon exposure to water. Increased swelling wasexpected to also improve the deinking properties of the resin.

Examination of potential resin compositions using Quantitative StructureProperty Relationship (QSPR) calculations resulted in possible resinformulations using the dimer acid reacted with one or a combination ofdiamines; phenylenediamine, PACM-20 (Air Products), andhexamethylenediamine, and either of two amino acids; (L)-tyrosine and(L)-glutamic acid. The dimer acid may vary from that depicted above toinclude about five —CH₂— carbons groups less to about five carbon groupsmore on each of the alkyl arms and about three carbon groups less toabout five carbon groups more on the carboxylic acid arms, as well as amixture of various dimer acids. A rigid diamine such as that representedby PACM-20 (bis(4-aminocyclohexyl)methane) is preferred and gives goodproperties. The dimer acid used herein was EMPOL-1018 (not hydrogenated)obtained from Cognis. Molecular modeling and experimental work showedthat the combination of a diamine, a dimer acid, and an amino acidresulted in a resin that was too brittle. To minimize this problem, theC-6 diacid, adipic acid, was added. This molecule was expected to aid inimparting some toughness into the soy-based polymer. The model alsopredicted a lower glass transition temperature. A glass transitiontemperature in the range of 55-70° C. is well suited to the processingand performance of toners.

A preferred ratio for diamine/dimer acid is between 1 and 2. Mostpreferably between 1.8 and 1. The material obtained should haverelatively lower degrees of polymerization compared to typical highpolymers, more on the order of that found in oligomers.

Experimental protocol consisted of combining the components in areaction flask equipped with an overhead stirrer, argon/vacuum inlet,and thermometer. The mixture was heated at 260° C. for two hours. Asteady stream of argon was employed to remove the water vapor producedduring the condensation polymerization. After two hours, vacuum wasapplied, while keeping the temperature at 260° C., for an additional twohours.

Analytical tests were performed on samples of each resin to determineviscosity and glass transition temperature. Details about thecomposition were confirmed using infrared spectroscopy (IR) and nuclearmagnetic resonance spectroscopy (NMR). Swelling measurements werecarried out on select samples at pH 7 and pH 10, at 50° C. A basiccondition was chosen to see if higher pH was more effective in swellingthe polymer than a neutral pH.

Fifteen different resin compositions were prepared (see Table 1 andTable 2 below). The initial resin composition contained dimer acid,PACM-20, and (L)-tyrosine. However, under the reaction conditions, the(L)-tyrosine sublimed out of the reaction vessel. Infrared spectroscopyanalysis indicated that no (L)-tyrosine was incorporated into the resin.This conclusion was supported by the thermal analysis data, which showedno change in the glass transition temperature (Tg) between this resinand the control (dimer acid and PACM-20 only). Because of the failure toincorporate (L)-tyrosine into the polymer, (L)-glutamic acid was used inall subsequent resin formulations. A similar problem was encounteredwhen using phenylene-diamine and hexamethylenediamine as the diaminecomponent. Each sublimed out of the reaction flask, thus upsetting thestoichiometry of the polymerization. PACM-20 was found to be a moresuitable diamine, as it has a higher boiling point.

A resin that consisted of a 1.0:2.5:1.0:0.5 ratio of dimer acid,PACM-20, (L)-glutamic acid, and adipic acid was chosen for initial testsof toner preparation and performance. The resin (34-8) had a Tg of 88.4°C. and a melt viscosity of around 3.7×10² P at 190° C. A toner wasprepared using this resin, but problems were encountered due to thebrittleness of the polymer. To alleviate this, soy protein isolate wasblended with a second batch of the same resin. This batch of polyamideresin (50-17) had a lower Tg at 80.3° C. and a viscosity around 1.3×10²P at 190° C. The addition of the soy protein isolate raised the Tgslightly and also resulted in shear thinning versus shear-independentviscosity behavior (52-22). No previous resins had demonstrated thisproperty. Another noticeable change caused by the addition of the soyprotein was seen in the results of the swelling measurements. The resinitself only swelled 1-2% after three days at 50° C. in a water bath atboth pH 7 and pH 10. The resin, with the incorporated protein, swelled7% under the same conditions although this measurement was low since thesample had partially disintegrated in the water bath. It was anticipatedthat the breakdown of the polymer was a possible predictor of howreadily the toner could be removed from paper.

Three batches of black toner were made using the resin blended with 20%soy protein isolate. The resulting paper copies were then tested forextent of deinking. A description of the toner preparation and thedeinking tests along with a more detailed discussion of the results canbe found in the subsequent sections of this report.

TABLE 1 Polyamide based Toner Resins Molar Ratio of SampleDimerAcid:Diamine:AminoAcid:Adipic Number Diamine Amino Acid OtherAdditive Acid Additive  4-22 PACM-20 Tyrosine none 0.5:1:1  6-24 PACM-20none none 0.5:1 12-6  Phenylenediamine Glutamic Acid none 0.5:1:0.315-30 PACM-20 Glutamic Acid none 0.5:1:0.2 27-23 PACM-20 Glutamic AcidAdipic Acid 0.5:0.8:0.2:0.2 30-17 PACM-20 Glutamic Acid Adipic Acid1:3:1:1 34-8  PACM-20 Glutamic Acid Adipic Acid 1:2.5:1.0:0.5 36-24PACM-20 Glutamic Acid Adipic Acid 1.4:3.0:1:0.2 50-20 PACM-20 GlutamicAcid Adipic Acid 0.9:2:1.2:0.13 52-17 repeat of 34-8 52-22 (52- PACM-20Glutamic Acid Adipic Acid + 1:2.5:1.0:0.5 + 17 with Blended Soy (blendedsoy protein Soy Protein Protein Isolate isolate at 20% by Isolate)weight) 54-13 hexamethylenediamine Glutamic Acid Adipic Acid1:2.5:1.0:0.5 56-19 hexamethylenediamine Glutamic Acid Adipic Acid0.5:0.63:0.63:0.5:0.25 and PACM-20 63-10 scale-up of 34-8 65-20 scale-upof 34-8 67-6  scale-up of 34-8 70-14 repeat of 34-8 72-9  repeat of 34-874-10 repeat of 34-8 80-30 PACM-20 1:1 81-31 PACM-20 1.05:1 84-20PACM-20 1.25:1 91-5  scale-up of 36-24 1.4:3:1:0.2 93-10 scale-up of36-24 1.4:3:1:0.2 95-6  scale-up of 36-24 1.4:3:1:0.2 1-3-10 scale-up of36-24 1.4:3:1:0.2 1-4-29 scale-up of 36-24 1.4:3:1:0.2 1-9-6 scale-up of36-24 1.4:3:1:0.2 1-12-7 scale-up of 36-24 1.4:3:1:0.2 1-13-25 scale-upof 36-24 1.4:3:1:0.2 1-17-1 scale-up of 36-24 1.4:3:1:0.2 1-17-27scale-up of 36-24 1.4:3:1:0.2 1-20-19 scale-up of 36-24 1.4:3:1:0.2 AllPolyamide resins were made with dimer acids typically made from soybeanoil. In the present case the dimer acid used was COGNIS-1018 (nothydrogenated). The dimer acid typically has two carboxylic acid groupsand two hydroxyl groups.

TABLE 2 Summary of Results of Polyamide Toner Resins Swelling ResultsGlass Transition (50° C. for 72 hrs.)/ Sample Temperature (Tg)Approximate % change in Number (° C.) Viscosity (Poise) Comments mass 4-22 34.4 NA Amino acid sublimed  6-24 33.7 NA pH 7 = 1.73 pH 10 = 4.5712-6  Inconclusive NA Diamine sublimed 15-30 Inconclusive NA 27-23 75.2NA 30-17 97.4 9.0 × 10³ pH 7 = 2.36 pH 10 = 1.98 34-8  88.4 3.7 × 10² pH7 = 2.07 pH 10 = 1.64 36-24 72.5 1.6 × 10² pH 7 = 1.53 pH 10 = 1.6750-20 80.9 1.0 × 10² 52-17 80.3 1.3 × 10² 52-22 82.8 viscosity is a pH 7= 7.6 function of shear (disintegrated) rate pH 10 = 8.3 54-13Inconclusive 5.5 × 10² Diamine sublimed 56-19 Inconclusive 1.0 × 10²Diamine sublimed pH 7 = 10.0 pH 10 = 5.0 63-10 80.2 NA 65-20 85.0 2.1 ×10² 67-6  84.1 1.0 × 10² 70-14 80.7 1.8 × 10² 72-9  79   1.1 × 10² 74-1080.5 2.5 × 10² 80-30 57.0 81-31 45.9 84-30 19.4 91-5  93-10 95-6  1-3-101-4-29 1-9-6 1-12-7 1-13-25 1-17-1 1-17-27 1-20-19

Referring again to Table 2, it is noted that rheology data is typicallyrepresented by plotting viscosity versus shear rate. In the interest oftime and space, an approximate value is reported for all samples thathave a viscosity independent of the shear rate (thus, the graph is arelatively straight line.) The only sample where this is not true is theresin blend of 20% soy protein isolate (52-22). In this case, theviscosity is a function of the shear rate and therefore, cannot beexpressed as a single value. The viscosities were measured at 190° C. ona Rheometrics SR5 apparatus. The materials were Newtonian over a shearrate range of 10⁻¹ to 10² reciprocal seconds. Swelling results wereobtained by placing the toner into an aqueous buffered solution athe thespecified pH for 72 hours at 50° C. The swelling results are reported asan increase in mass in weight %. Sample 52-22 having the protein isolateincorporated disintegrated under those conditions at a near neutral pHof about 7.6.

The 14 samples from 80-30 through 1-20-19 represent scale ups ofmaterial productions compared to the other samples. Scale up was by afactor of about 4.5.

Toner Preparation and Copier Evaluation

A Toshiba Model 1360, a small desktop copier with a copy output of 13copies per minute, was used as a test copier for comparing results withconventional toners and the toners of the present invention. This copieruses an organic photoconductor with a two-component magnetic brushdevelopment system and requires a positive charging toner.

Determination of Developer System

An experimental developer system using 6% conventional toner on aPowdertech FBF-300 carrier was evaluated to confirm that this systemcould be used to produce images that were on par with the commerciallypurchased developer package for this copier. The test developer systemgave a toner triboelectric charge of 13 microCoulomb/gm and producedcopies that were subjectively judged to be equivalent to copies producedby the conventional developer system. Based on these results thestandard for experimental developers system was 6% toner on FBF-300.

Preparation and Evaluation of Test Toners

Toner compositions were prepared based on soy polymers that wouldfunction in the Toshiba 1360 and could be used to produce copies (100 to200 copies) for the deinking tests. There are a number of polymerproperties that are critical for toner performance. However, since thepurpose was to demonstrate that soy polymer-based toners provideimproved deinking over conventional toners, three key properties wereselected that are fundamental for short term toner performance to allowthe preparation of a limited number of copies. The key properties thatwere focused on were:

Positive triboelectric charge with a target of 10 to 20 microCoulomb/gm.A positive triboelectric charge is required to produce a copy and imagequality is affected by the magnitude of the charge.

Polymer glass transition temperature (Tg) with a target of 55° C. to 70°C. Acceptable fusing and blocking resistance (i.e. toner powder cakingon storage) is strongly influenced by Tg.

Toner particle size and size distribution with a mean of 8 μm to 12 μmas the target with 95% in the range from 5 μm to 20 μm. Imagingperformance and development life is affected by size and sizedistribution.

A basic toner composition of 10% carbon and 90% polymer was used. Otheradditives noted below may be included in typical toners to obtaindesired toner performance:

Knowing the teachings of the invention, those skilled in the art areable to select additives and materials to obtain desired the chargeproperties.Flow control agents—to provide good powder flow.Surface Additives—typically lubricants to prevent toner offset to thefuser rolls, cleaning aids, triboelectric charging; toner flow andhandling; e.g. Aerosil (R972), Titania (P25) to provides triboelectriccharge stability, zinc stearate acts as a charge rate improver and as ablade cleaner lubricant;kynar (fluoropolymer)—as a lubricating additive.Colorants—black, e.g. carbon black, magnetite, or a combination of both,highlight color, full color gamut; typical colorpigments—cyan—substituted metallo phthalocyanines,Magenta—quinacridones, azonapthols, aminofluorenes (xanthenes), yellow,bisazo derivatives of diaminobiphenyl, monoazo compounds.Bulk additives—fusing and release promoters, e.g. wax.Magnetic additives—typically for toner containment, developmentproperties, color, cleaning.Conductive and nonconductive additives—typically added to control tonerconductivityCharge Control Agents—added to provide the correct sign and magnitude oftriboelectric charge; for controlled charging rate; fusing parametersand fuser life; e.g. higher styrene content in the thermoplastic polymerleads to more negative charging.

Typical thermoplastic polymers (and their monomers) useful with theinvention include polyamides, polyesters, polyester ethers, styreneacrylates, polyurethanes, and mixtures thereof. As noted herein styrenecopolymers with increased amounts of styrene may be useful for attainingnegative charges. The materials provide enhanced properties whenprepared according to the teachings of the invention.

Proteins useful with the invention may be derived from animal or plantsources such as soya protein, zein, collagen, casein, protein albumen,fish proteins and the like. The soy isolate proteins used hereintypically had a protein content of about

Mixture as used herein can be a collection of components or materialswhere they are substantially uniformly dispersed; typically since oneingredient is a thermoplastic polymer the components or materials aremelt blended together.

Degree of polymerization—it has been found by tests herein that the bestmaterials have a degree of polymerization that provides a solid tonermaterial at room temperature yet processes easily and quickly at typicaltoner temperatures. The materials should flow easily onto paper or othersubstrate and adhere well upon being heated above their Tg. Typicaldegrees of polymerization include 5-50 units. The material should not bebrittle so as to break up and produce unwanted flakes or dust.

The ratio of rigid diamine to dimer acid is preferably between 1 and 2and most preferably between 1 and 1.8. Lower molecular weight materialsare preferred that are in the polymerization range typically attributedto oligomers or lower molecular weight polymers. This provides materialshaving proper physical characteristics for toner performance.

In addition, blends of different molecular weight polymers may be usedto provide the desired melt rheology for acceptable fusing behavior. Inthe examples herein the additives used were minimized; in general, fumedsilica was added to aid in powder flow to achieve good magnetic brushformation. The basic toner composition used throughout was 90% resin and10% carbon black. Regal 330, a typical carbon black used forelectrophotographic toners, was used for all experimental toners.

Typical thermoplastic polyamides prepared according to the inventioninclude those made from Dimer acid (e.g. EMPOL-1018); Diamine (e.g.rigid diamine such as PACM-20 and the like); Dibasic Amino Acid ((e.g.glutamic acid, aspartic acid and the like); and Aliphatic diacid (e.g.adipic acid, melonic acid, glutaric acid, and the like). In some typicalapplications the polyamide is obtained by reacting a protein isolatedirectly with the dimer acid, aliphatic acid and diamine.

Preparation of Copies for Deinking Tests

Three separate groups of copies were tested for deinking properties.

First Sample Set for Deinking Evaluation

The initial set of copies for deinking was produced using thetoner/developer systems shown in Table 3. This set included threeexperiment soy-based systems and two conventional controls. As thistable shows, the image density of the experimental toners were all lowerthan that produced by the conventional developer/toner system (0.6compared to 1.4). Since this image density difference could bias thedeinking results the second conventional control was produced at a lowerimage density setting to obtain an image density (0.7) comparable to thecopies produced from the experimental toner. These copies were producedthe conventional carrier (FBF-300) was obtained and identified. Forthese evaluations, a experimental proprietary carrier and anconventional carrier that had been washed to remove the conventionaltoner were used. It was confirmed, by evaluating washed conventionalcarrier with conventional toner, (i.e. conventional toner was added tothe washed conventional carrier and produced equivalent image quality tothe original conventional system) that the function of the conventionalcarrier was not substantially affected by the washing procedure. None ofthe experimental toners shown in Table 3 were classified to obtain thenarrow particle size distribution that is needed for optimalperformance. As a result, the images produced had high background (i.e.toner deposited in non imager areas). As an additional control to assessthe impact of toner background on the deinking result, the copies forsample E were made without an original document on the copier platen.This procedure allowed the production of copies with only backgroundtoner.

TABLE 3 First Sample Set for Deinking Evaluations Toner Composition(pbw) (2) Developer System Poly Procoat % Triboelectric Polymer amide(soy Fumed charge Sample ID Toner ID Soy Polymer ID (1) Tg (° C.) resinIsolate) Unirez2662 Carrier Silica μcoulombs/gm Image Density A CON — 00 0 CON 0 11 1.4 A CON — 0 0 0 CON 0 11 0.7 D 48402-02-01 34-08 88 90 00 XC-1283-51 0 29 0.6 C 48402-23-01 34-08 88 75 0 15 Washed 0 45 0.6 CONB 48402-36- 52-17 80 72 18 0 Washed 2 39 0.7 01* CON E 48402-36- 52-1780 72 18 0 Washed 2 39 — 01* CON Note (1) - The reactant ratios for thesoy based polyamide resin used were: Dimer acid - 33.3 pbw PACM-20(diamine) - 41.7 pbw Glutamic acid - 16.7 pbw Adipic acid - 8.3 pbw Thisgives a molar ratio of 1:2.5:1.0:0.5 (dimer acid:PACM-20:glutamicacid:adipic acid). (pbw) = parts by weight CON = conventional Note (2) -All experimental toners contained 10 pbw carbon black (Regal 330).*Designated as soybean derived toner composed of polyamide resin andprotein isolate.

Two approaches to improve deinking were explored with these experimentaltoners. The first approach is demonstrated by samples C and D. Thetoners used to produce these copies are based on using a soy polymer asa replacement for the typical toner polymer. Since the polyamide resinwas very brittle, 15 pbw Unirez 2662 (commercial polyamide resin) wasadded to the toner formulation used for sample C in an attempt to obtaina tougher toner and reduce the fines generated during the grinding step.This did not work. The second approach is shown by sample B, which useda soy based polymer with soy isolate as an additive (designated assoybean derived toner). The concept with this approach was to createadditional swelling of the toner particles due to the presence of thesoy isolate. The bench top swelling tests confirmed significantly higherswelling due to the addition of the soy isolate.

The results of the deinking tests will be discussed below.

Second Sample Set for Deinking Evaluation

The second set of copies for deinking was produced using thetoner/developer systems shown in Table 4. As this table shows, controlcopies produced using the conventional (CON) developer system wereincluded with this set. The major goal of this work was to repeat andconfirm improved deinking performance as a result of the addition of soyisolate. Sample B-1 is basically a repeat of sample B from the initialdeinking tests. However, due to the relatively high Tg (84° C.) thecopies were not well fused. As previously indicated, the preferred Tgfor a toner polymer is in the range of 55° C. to 70° C. Before thedeinking evaluation was carried out the copies were post fused. Inaddition, an experimental toner was prepared by melt blending soyisolate with the conventional toner. If the addition of soy isolatealone will provide improved deinking, then conventional tonermanufacturers could potentially modify their existing toners to obtainimproved deinking. Toner manufacturers would probably be more willing toconsider this type of change; that is, a soy-based additive to improvedeinking rather than the more complex change of the toner polymer. Theexperimental toners used for this set of evaluation were all classifiedto obtain a narrower particle size distribution that was a betterapproximation of the conventional toner

TABLE 4 Second Sample Set for Deinking Evaluations Toner Composition(pbw) (2) Soy Procoat Triboelectric Particle Size Sample Toner ResinPolymer CON Poly- (soy Developer charge Image Mean ID ID ID 1) Tg (° C.)Toner amide Isolate) Carrier μcoulombs/gm Density (μm) % 5-20 μm C1 CON— — 0 0 0 CON 11 1.3 12 95 B1 48402-52-01 — — 72 0 18 FBF-300 13 1.4 1184 A1(3) 48402-55-01 67-06 84 0 72 18 FBF-300 10 1.0 10 79 Note 1) - Thereactant ratios for the soy polymer used were: Dimer acid - 33.3 pbwPACM-20 (diamine) 41.7 pbw Glutamic acid - 16.7 pbw Adipic acid - 8.3pbw This gives a molar ratio of 1:2.5:1.0:0.5 (dimeracid:PACM:glutamatic acid:adipic acid). Note (2) - All experiencedtoners contained 10 pbw carbon black (Regal 330). Note (3) - Post fusedat 220° C. for 6 seconds.

Third Sample Set for Deinking Evaluation

The third set of copies for deinking was produced using thetoner/developer systems shown in Table 5. Again the experimental tonerswere all classified to obtain a particle size distribution more typicalof a commercial toner. However, the classification of toner 48402-64-01used to produce the copies identified as D-2 was not very successful, asindicated by the low percentage (41%) of particles in the 5 to 20 μmrange.

The purpose of this set of samples for deinking evaluation was todetermine the impact of post fusing on the deinking results and evaluatethe impact of a higher concentration of soy isolate in the conventionaltoner on deinking. As previously indicated the details of the deinkingresults will be presented in a later section.

Deinking Tests

This section summarizes results from deinking tests (Task 5) conductedat North Carolina State University under a confidentiality agreement.The main objective of this task was to establish improved deinkabilityof prints made with soy toner compared to that of a regular toner usinga laboratory chemical deinking procedure. Printed papers imaged withtoners were pulped in a laboratory mixer using a standard surfactant.Pulped fibers were washed and further treated in a flotation cell tofurther remove toners separated from the printed-paper. Hand sheets weremade with pulp before and after flotation process. Brightness and dirtcount were measured to assess how well the toned images were deinked.

A typical deinking experiment and analysis of hand sheets is describedbelow:

1. The samples (pieces about 5×5 cm) were soaked in the water (50° C.)for 10 min.2. Sample was taken from the jar and put into a laboratory mixer(Waring, Commercial, Model 47 BL84(CB6) Heavy Duty Blender).

TABLE 5 Third Sample Set For Deinking Evaluations Toner Composition(pbw) (2) Procoat Triboelectric Particle Size Soy Resin Polymer CONPoly- (soy Developer charge Image Mean Sample ID Toner ID ID (1) Tg (°C.) Toner amide isolate) Carrier μcoulombs/gm Density (μm) % 5-20 μm A2CON — 0 0 0 CON 11 1.3 12 95 C2 - (3) CON — — 0 0 0 CON 11 1.0 12 95 D248402-64-01 — — 62.5 0 37.5 FBF-300 na 0.6 14 41 B2 48402-67-0170-14/72-09 80 0 72 18 FBF-300 na 0.7 13 67 E2 - (4) 48402-67-0170-14/72-09 80 0 72 18 FBF-300 na 0.5 13 67 Note (1) - The reactantratios for the soy polymer used was: Dimer acid - 33.3 pbw PACM-20(diamine) - 41.7 pbw Glutamic acid - 16.7 pbw Adipic acid - 8.3 pbw.This gives a molar ratio of 1:2.5:1.0:0.5 (dimer acid:PACM-20:glutamicacid:adipic acid). Note (2) - All experimental toners contained 10 pbwcarbon black (Regal 330). Note (3) - Reduced image density Note (4) -Post fused at 220° C. for 6 seconds.1. The repulping was done in the laboratory mixer @ a temperature of 50°C. at the lowest rpm.

2. Consistency was ca. 2.5%.

3. After 1 minute of repulping, the pH was adjusted with NaOH to thevalue of pH=10.0.4. Under alkaline conditions the repulping was continued for 4 minutes.5. The final temperature was 50° C., due to the heat generation of theagitation negating the heat loss to the surroundings.

Flotation

1. The flotation was performed in a laboratory-scale flotation cell(Adirondack, Formax™ Flotation Deinking Cell, 29.1 L) at a consistencyof approximately 0.7%.2. The temperature was adjusted with direct steam to 40° C. The slurrywas circulated in the flotation cell at 57 L/min. The feed sample wastaken.3. Non-ionic surfactant was added (Lionsurf 729, 0.125% on dry solids)and the slurry was allowed to circulate for 5 minutes.4. After 5 minutes of circulation, the air flow was opened with the rateof 225 L/min. The foam from the center of the flotation cell wascollected and weighed.5. After 10 min. of flotation, the air input was closed and the acceptssample was taken.

Methods

1. Handsheets from slurry before and after flotation were made inaccordance to TAPPI Standard T 205.2. Brightness was measured in accordance to TAPPI Standard T 452.3. Rejects were not diluted. The pads were formed by filtering thesample (ca., 75 mL) with a Buchner funnel (Whatman 42 Ashless FilterPaper).4. The solids were determined by drying the samples in a laboratory CEMLabWave 900 microwave.5. Image analysis was performed on an Apogee Spec*Scan 2000 analyzerwith 600 dpi scanner (HP Scanjet 3C, Hewlett Packard). The threshold fordetection was 120 and the smallest size detected was 0.01 mm². Thesmooth side (wire-side) of four sheets was used for each analysis.

The flotation process ran without problem. In general, the amount ofrejects taken from the flotation, the consistency of the rejects, andthe amount of foam was adequate and reasonably constant among allexperiments. Good agreement between duplicate runs was achieved.

Flotation efficiency was defined as:

Flotation Efficiency=100%*(1−PPM Accepts/PPM Feed)

Brightness and image analysis are complimentary and the use of bothenhances interpretation of the results. Brightness gain, which providesan indication of the removal of detached toner particles from the pulp,is a convenient and practical way to assess how well a toned image hasbeen deinked.

Deinking Results

Results from the first sample set for deinking evaluations for detailsof the toner and resin composition) are shown in Tables 3 and 6. Majorpoints worthy of note are:

Sample B hand sheets composed of pulped print paper made from polyamide(soy resin) and soy isolate (designated as soybean derived toner) basedtoner has a brightness value of 74.07-73.51 before flotation (designatedas “Before” sample) and is quite comparable to Sample E (with abrightness value of 74.48-71.22) that had no image. This suggests thatsoybean derived toner is removed (deinked) quite readily by simplepulping even prior to flotation process. Other samples (A, A reduced, Cand D) have “Before” brightness values in the 69.07-71.42 range preparedunder the same conditions.

Samples C and D (see Tables 3 and 6) that have a higher glass transitiontemperature (88° C.) appear to have poorer deinkabilty, as measured by“Before”brightness values (69.07-70.63 vs. 74.07-73.51 for Sample B) ofpulped sample prior to flotation compared to Sample B that has a glasstransition temperature of 80° C. It appears polyamide with higher glasstransition temperature has reduced deinkability after washing andpulping prior to flotation.

Brightness values after flotation show further improvement with allsamples. However, the largest improvement is seen for Sample A (controltoner at a print density of 1.4 0). This suggests that simple washingand pulping will not deink print images made with standard toners and aflotation process would be required to achieve adequate deinking. Thehighest brightness is seen with Sample B (images made with soybeanderived toner) amongst the other samples at a lower image density of0.6-0.7.

Dirt count of pulp is quite low for Sample B similar to rest of the lowimage density samples compared to Sample A prior to flotation process.Rest of the data (rejects and solids in reject) is quite comparable inall the samples.

The above results suggest that toner according to the invention appearsto be more readily deinkable than a conventional toner, as judged by itsease of removal from the printed copy paper by a simple pulping followedby washing process and not requiring the normal flotation step used inthe deinking of regular electrostatic printed copy paper. The resultsare somewhat tentative due to the fact that the image density of printsmade with soybean derived toner are less than what is typical ofconventional toners. Further, brightness values noted for Sample B andcontrol, even though appear to be real, do not differ by a large amount.A toner that has the easy deinkability as a built in feature like SampleB would offer significant cost savings in capital equipment and processcosts in the production of secondary fibers from office copy papers.

Results from the second round of deinking tests are shown in Table 7. Inthis set of tests the objective was to check the reproducibility ofready deinkability noted with soybean derived toner after the imageswere post fused in an oven to make sure that the toner was fully meltedand fixed in the paper (Sample A1). This test was performed as there wassome concern that ready deinkability seen with Sample B in the firstround of deinking study could be influenced by poor fusing of the tonedimage due to its slightly higher glass transition temperature. Furtherit was desired to evaluate if addition of soy protein isolate (SampleB1) to the control toner (Sample C1) would promote its readydeinkabilty.

Major findings from these examples were that there was a small butsignificant increase in “Before” brightness value of sheets made fromwashed and pulped copy paper prior to flotation in soybean derived tonerSample A1 (value of 72.41-71.86) compared to Control Toner C1 (value of70.36-70.18) and soy isolate containing Control Toner B1 (value of70.31-70.66). The lower brightness observed for Sample A1 (72.41-71.86)in this set compared to a value of 74.07-73.51 for Sample B in the firstset data suggest that post fusing sample has fixed the toner moretightly, thus making its removal more difficult by washing and pulping.All the “Before” samples had lower brightness values than those seen inthe first round of testing. Addition of soy isolate to the control tonerdoes not appear to help in easier deinking of the control toner bysimple washing and pulping. Brightness results of “Before” samples areencouraging as it confirms the finding from the first round of testingthat soybean derived toner can be deinked by washing and pulping withouthaving to use the expensive flotation process.

Third round of deinking tests were done to further confirm differencesin deinking performance that had been observed with soybean derivedtoner in the previous two rounds of deinking tests. Results are shown inTable 8. Samples A2 and C2 correspond to control toners with normalimage density and reduced image density. These two samples are repeatsamples A and “A reduced” in Table 6 from the first round of testing.

Sample D2 has soy isolate at 37.5% loading in the control toner comparedto the normal loading of 18% in “soybean derived toner designated as B2and E2. Sample B2 corresponds to sample B of Table 6 from the firstround of testing and Sample E2 corresponds to Sample A1 from Table 7from second round of testing. Sample E2 represents normal soybeanderived toner after post fusing.

Major findings worth noting are:

As observed in the first round of testing, normal soybean derived tonerscontaining 18% soy isolate (Samples B2 and specifically E2) had thehighest “Before” brightness values after washing and pulping prior toflotation and were better than the control toner at high image density(Sample A2). Control Toner (Sample C2) at reduced density had brightnessvalues comparable to Sample B2 before flotation.

Sample E2 (soybean derived toner after fusing) showed the highest“Before” brightness value (73.8-75.47) and was better than the valueobtained with “no post fusing” sample (Sample B2 with a value of71.31-70.62). This result was not totally expected, as one would haveexpected reduced ease of deinkability with a post fused image. It isworth noting that glass transition of polyamides used in Sample B of thefirst set (Table 3) and Samples B2 and E2 of the third set (Table 5)were 80° C. and that of A1 used in the second set (Table 4) was slightlyhigher at 84° C.

All the samples showed further improvement in brightness afterflotation.

TABLE 6 First Set Deinking Tests LABORATORY FLOTATION Pulp Brightnessand Reject Data: PULP PULP REJECT Brightness (°GE) Gain Image AnalysisResults (PPM) Weight Solids Solids Brightness Sample Run # Before STDVAfter STDV (%) Before After Rem. Eff. (%) (g) (%) (% of furnish) (°GE)STDV A 1 70.22 0.41 78.62 0.26 11.96 190 6 97 535.1 2.94 7.87 62.21 0.242 70.07 0.39 78.46 0.31 11.97 180 13 93 515.7 3.21 8.28 69.29 0.16 B 174.07 0.27 77.58 0.55 4.74 13 10 23 497.7 2.69 7.44 58.22 0.61 2 73.510.36 77.38 0.51 5.26 4 0 100 409.6 2.85 6.49 60.69 0.10 C 1 70.18 0.3673.96 0.30 5.39 30 5 83 410.8 2.75 5.65 64.30 0.25 2 70.63 0.35 74.800.34 5.90 20 5 75 574.9 3.38 9.72 64.66 0.39 D 1 69.07 0.35 73.17 0.275.94 56 5 91 438.2 2.76 6.05 61.01 0.56 2 69.51 0.33 73.13 0.30 5.21 316 81 361.9 3.42 6.19 60.04 0.38 E 1 74.48 0.29 75.52 0.73 1.40 12 6 50806.0 2.78 11.20 70.01 0.44 2 71.22 0.59 72.33 0.24 1.56 7 2 71 471.73.33 7.85 67.57 0.62 A 1 71.42 0.30 75.62 0.27 5.88 17 1 94 556.2 3.6010.01 66.28 2.35 Reduced 2 71.16 1.05 75.58 0.24 6.21 8 2 74 508.2 3.428.69 68.64 1.27 SOLIDS IN REJECT (%) Measurement Sample Run # 1 2 AVRG A1 2.93 2.94 2.94 2 3.22 3.19 3.21 B 1 2.68 2.70 2.69 2 2.84 2.86 2.85 C1 2.73 2.76 2.75 2 3.35 3.41 3.38 D 1 2.77 2.75 2.76 2 3.42 3.41 3.42 E1 2.79 2.76 2.78 2 3.33 3.33 3.33 A 1 3.22 3.98 3.60 Reduced 2 3.28 3.553.42 NOTE Furnish per run = 200 g a.d. pulp (run “B” only 180 g a.d.)

TABLE 7 SECOND SET DEINKING TESTS* LABORATORY FLOTATION Furnish per run= 200 g a.d. pulp REJECT PULP Solids Brightness (°GE) Gain Weight Solids(% of Brightness Specific Brightness Gain SAMPLE RUN # Before STDV AfterSTDV (%) (g) (%) furnish) (°GE) STDV (% per % of solids in reject)Average A1 1 71.86 0.95 74.94 0.31 4.29 765.1 3.06 11.71 66.41 1.010.366 0.340 2 72.41 0.96 75.21 0.15 3.87 779.5 3.17 12.36 66.44 0.790.313 B1 1 70.31 0.50 75.04 1.09 6.73 620.0 3.16 10.88 58.07 0.81 0.6180.700 2 70.66 0.43 77.03 0.21 9.02 847.3 2.45 11.53 60.66 0.41 0.782 C11 70.36 0.25 77.41 0.21 10.02 846.6 3.16 13.38 63.05 0.37 0.749 0.718 270.18 0.25 77.40 0.22 10.29 984.6 3.04 14.97 65.16 0.79 0.687 SOLIDS INREJECT (%) DIRT COUNT OF PULP (PPM) Measurement Flotation SAMPLE RUN # 12 AVRG SAMPLE RUN # Before After Eff. % A1 1 3.06 3.05 3.06 A1 1 89.1012.70 85.7 2 3.18 3.15 3.17 2 77.70 19.60 74.8 B1 1 3.16 3.15 3.16 B1 11631.40 50.80 96.9 2 2.38 2.52 2.45 2 1606.20 48.60 97.0 C1 1 3.14 3.173.16 C1 1 135.50 5.50 95.9 2 3.02 3.05 3.04 2 131.30 7.60 94.2 *Resultsfrom the three sets of deinking tests show that there is a definitetendency for the soybean derived toner to deink more readily afterwashing and pulping prior to flotation compared to the control tonerused in the Toshiba copier. Actual degree of ready deinkability tendencyof soybean derived toner, as measured by “Before” brightness value ofhand sheets made with pulp after washing and pulping prior to flotation,appears to vary in the three deinking tests. Deinkabilty of soybeanderived toner appear to depend on factors such as image density, postfusing of image, differences in the glass transition temperature ofpolyamide, particle size and classification of toners and inherentvariability in the deinking test procedure. It would be very useful toevaluate some of these factors in a systematic study in a follow-onproject to fully define and quantify these preliminary promising resultsthat show easier deinkability of office copy paper printed with soytoner like soybean derived toner.

TABLE 8 Third Set Deinking Tests PULP REJECT Specific Brightness GainBrightness (°GE) Gain Weight Solids Solids Brightness (% per Sample RunBefore STDV After STDV (%) (g) (%) (% of furnish) (°GE) STDV % of solidsin reject) Average A2 1 68.20 0.53 76.65 0.30 12.39 490.2 1.44 3.5341.64 0.41 3.51 3.22 2 67.60 0.80 76.94 0.35 13.82 467.8 2.01 4.70 44.981.26 2.94 B2 1 71.31 0.39 75.97 0.59 6.53 460.3 1.96 5.01 58.53 0.311.30 1.44 2 70.62 0.58 75.48 0.80 6.88 488.2 1.60 4.34 60.37 1.65 1.59C2 1 71.49 0.62 78.59 0.52 9.93 434.3 2.19 4.76 59.59 1.08 2.09 2.05 272.96 0.79 78.77 0.47 7.96 458.1 1.73 3.96 56.76 1.54 2.01 D2 1 70.460.38 74.39 0.67 5.58 430.6 2.26 5.41 55.72 2.61 1.03 1.14 2 69.59 0.6274.52 0.68 7.08 499.4 2.04 5.66 60.80 2.43 1.25 E2 1 73.80 0.90 77.060.45 4.42 481.8 2.26 6.05 61.97 0.32 0.73 0.52 2 75.47 0.56 76.92 0.491.92 691.4 1.65 6.34 64.32 0.57 0.30 SOLIDS IN REJECT (%) DIRT COUNT(PPM) Measurement Flotation Efficiency Sample Run # 1 2 Avrf Sample Run# Before After % Average A2 1 1.43 1.45 1.44 A2 1 87.80 3.30 96.24 92.462 1.99 2.02 2.01 2 134.20 15.20 88.67 B2 1 1.96 1.96 1.96 B2 1 8.20 1.3084.15 81.30 2 1.59 1.61 1.60 2 13.00 2.80 78.46 C2 1 2.20 2.18 2.19 C2 15.30 2.10 60.38 73.74 2 1.71 1.74 1.73 2 9.30 1.20 87.10 D2 1 2.26 2.252.26 D2 1 28.50 3.60 87.37 91.25 2 2.02 2.05 2.04 2 20.50 1.00 95.12 E21 2.27 2.24 2.26 E2 1 15.40 3.10 79.87 89.94 2 1.64 1.65 1.65 2 6.200.00 100.00

The present invention does not require the deployment of a flotationprocess. Avoidance of the flotation step would have a significant costsavings estimated to be about 25% (both capital and operating) to asecondary fiber mill treating office waste paper. There could be addedenvironmental benefit for a readily deinkable toner technology based ona renewable resource such as soybean.

Polyamides based on dimer acid and isolate appear to have desirableproperties such as triboelectric charging, pigment compatibility,toughness for proper grinding and particle size classification and waterswelling needed in a readily deinkable toner.

Electrostatic soybean derived toners based on polyamide derived fromdimer acid and soy protein isolate perform well in a commercial Toshibacopier using a standard magnetic carrier. Copy quality of prints madewith soybean derived toner, even though adequate, requires furtherimprovement in image density.

Laboratory deinking tests show that copies made from soybean derivedtoners are more readily deinked in the washing and pulping process stepsin a conventional flotation deinking process compared to the copies madefrom a conventional electrostatic toner used in a Toshiba Copier. Actualdegree of ready deinkability of soybean derived toner appears to dependon factors such as image density, glass transition temperature of thetoner resin, particle size of toner, and other operating parameters

Laboratory deinking data suggests that there is a potential to eliminateor minimize the load on the capital intensive flotation process withplant and animal source derived toners.

The following sections 1 through 6 provide examples for the preparationand characterization of several toner formulations. One of theobjectives of the examples in Sections 1 through 6 was to preparenegatively charged toner formulations. The samples prepared belowconfirmed procedures for positively charged materials that wereprepared. In addition, the results provide guidance for obtainingnegatively charged materials by proper selection of negative chargecontrol agents or by control of monomeric ingredients in forming thethermoplastic polymer (e.g. additional styrene units).

Section 1 Preparation of Several Toner Formulations

This section illustrates the formulation and preparation of colored (inthese examples, black) “pseudo toners” based on combinations ofsoy-based polyester (synthesized according to the procedures describedherein) and a soy based protein (Procote 200 from Dupont). For theexamples herein these “pseudo toners would then be converted into“working toners” using surface blended fumed silica surface additives.

Pseudo toners are defined as not fully formulated toners lackingadditives typically added for “commercial or working toners” such asflow aids, the right level of control agents, anticaking agents and soon. Typical specifications for the working toners were derived from theCanon Optra C color toners used in the Lexmark Optra C color printersince this printer was used for tests.

Particle size:

Mean D₅₀˜8.5 μm

D ₉₀ /D ₅₀=1.35 or better

D ₅₀ /D ₁₀=1.35 or better

Triboelectric charge properties: Q/M=˜−25 μC/gram

Against a standard two component carrier silicone coated ferrite at 4%TC

Q/M=˜−10 to −12 μC/gram as measured directly off the aluminum developerroller of the Optra C developer cartridge

The main reasons for choosing the Optra C cartridge as a test vehiclefor toner were as follows: Toner samples for testing are relatively easyto introduce into this cartridge; the cartridge is relatively easy toclean up between toner samples under test; and the cartridges arereadily available at low cost.

Experimental toners that meet the size and triboelectric chargespecifications can be used in the cartridge in a Lexmark printer thathas had its fuser disabled, so that unfused images of known mass perunit area can be prepared for testing of fusing parameters, such asminimum fixing temperature, hot offset temperature, and fusing latitudefor various print speeds. The Lexmark Optra C printer is typical ofmodern color laser printers based on discharge area development andnon-magnetic single component development physics. As such it usesnegatively charging toner typical of modern laser printers and digitalcopiers.

First Pseudo Toner Prepared:

The first toner prepared was according to Formulation 1:

Carbon Black (Regal 330) 10.0 Experimental Soy dimer acid polymer (apolyamide) 71.75 Soy Protein Dupont ProCote 200 17.25 CCA Spilon TRH 1.0TOTAL 100.0 Note: Spilon TRH is a powerful negative charge controladditive added to the bulk of the toner. It is a black chromium azocomplex. Regal 330 is a commonly employed relatively neutral carbonblack.

The toner was compounded in a single screw extruder and micronized in anAlpine air jet mill, and finally classified to the final particle sizedistribution using an elbow jet classifier. Yield of this toner was lowdue to multiple changes in melt blend and micronizer process conditions.Some difficulty was noted in getting a uniform blend of all components,however sufficient toner was accumulated to allow for a study oftriboelectric charging behavior. However the mean particle size of thetoner was ˜7.2 microns, lower than that specified. Particle sizedistribution was mainly within specifications

The “pseudo toner” was mixed with the standard silicone coated ferritecarrier at 4% toner concentration on the carrier and rolled for 45minutes to ensure equilibrium charge had been achieved. The tonercharged very rapidly against this carrier. Triboelectric chargemeasurement showed that the toner had charged very positively againstthis carrier, which is specifically designed to charge tonersnegatively.

The value obtained was +35.7 μC/gram. This is a very high positivenumber considering the type of carrier used. Despite this result, thetoner was surface treated by high shear blending with different levelsof a negative charge directing fumed silica (Cabosil TG 811F), to studythe effect of surface silica on the triboelectric charge behavior of thetoner.

Triboelectric charge Q/M of toner+2% surface blended silica TG811F=−16.2μC/g.

Triboelectric charge Q/M of toner+2.5% surface blended silicaTG811F=−15.0 μC/g.

These results are the same within experimental error of the measurement,and show that at 2% surface additive, complete coverage of silica hasbeen obtained, or at least there is no further value to adding moresilica. Note that the target value of −25 μC/gram could not be achieved.Despite this fact, the toner was evaluated in an OptraC cartridge. Keyfunctional parameters to achieve in the cartridge are the correct chargeand powder flow properties, as well as the metered loading of toner onthe aluminum development roller of the cartridge. The toner shouldcharge to Q/M=−10 to −12 μC/g and have a mass per unit area of toner onthe development roller M/A between 0.55 and 0.6 mg/cm².

The measured parameters were:

Q/M=−3 to −5 μC/g

M/A=0.25-0.30 mg/cm²

In addition it was noted that the toner flowed too well (like water) andcaused a lot of toner “dumping” and toner overflow from the cartridge.These symptoms are typically associated with insufficient triboelectriccharge on the toner, wrong sign toner, inability of the metering bladeto constrain the toner, and toner powder flow properties that are toogood.

The low value of triboelectric charge may indicate excessive wrong signtoner or very low charge toner, as the Q/M value is an average charge ofthe toner.

Conclusion from First Toner Formulation

It was concluded that some ingredient of the toner is causing the tonerto inherently charge very highly positive. It was suspected that thismight be the ProCote 200 soy protein.

In addition it was concluded that with this particular formulation,addition of high levels of negative directing fumed silica could notovercome the underlying positive charge sufficiently to drive theoverall charging of the toner to the desired level of ˜−25 μC/g.

Note: As a test of consistency with past results, a test of thetriboelectric charge properties of the OEM Canon cyan toner was made.

The following results were obtained:

Triboelectric charge Q/M of OEM cyan toner at 4% TC on silicone coatedferrite carrier=−24.1 μC/g

Triboelectric charge of OEM cyan toner on aluminum developer roller ofOptra C cartridge=−12.5 μC/g

Mass per unit area of OEM cyan toner on developer roller=0.55 mg/cm²

These results are entirely consistent with previous experience of theOEM toner and its performance in the Optra C cartridge.

Second Set of Black Toners

The following illustrates the preparation of formulations goal andrationale behind the second set of formulations was to try to achieve amore neutral or slightly negative “pseudo toner” that could be tuned to−25 μC/g using much lower levels (<<1%) of fumed silica.

Black Toner Formulation 2

Parts by weight Carbon Black (Acidic type Raven 1255) 10.0 ExperimentalSoy dimer acid polymer 70.00 Soy Protein Dupont ProCote 200 17.00 CCAAzo Spilon TRH 3.0 TOTAL 100.0

Black Toner Formulation 3

Carbon Black (Acidic type Raven 1255) 10.0 Experimental Soy dimer acidpolymer 78.5 Soy Protein Dupont ProCote 200 8.5 CCA Azo Spilon TRH 3.0TOTAL 100.0

In these formulations, the amount of negative charge control additivewas increased from 1% to a practical maximum (3%) and the Regal 330neutral carbon black was replaced with a much more negative acidiccarbon black. In addition, in the Formulation 3 the amount of ProCote200 was substantially reduced. These formulations were melt compoundedand subjected to micronization and classification.

While micronizing the formulations a strange phenomenon was noted.Normally once the air flow, pressure and feed rate, and othermicronization parameters are established, the toner exiting the systemhas a rather constant mean particle size. However, with these toners, itwas found that the toner mean size continued to increase gradually, andthe material remaining in the micronizer became very hard to grind. Thissuggests that the dispersion of one or more components in the toner isnot good and that this component is much harder to grind than the bulkof the composition. The problem was more severe in Formulation 2 asopposed to Formulation 3, where there is less ProCote 200

Visually, the larger material was gray rather than black. It is believedthat this material contains large particles of the ProCote 200 that havenot been adequately and finely dispersed in the toner composition, andthat do not contain the required amounts of carbon black or TRH.

The main material was classified to the required particle size. Thistime a mean particle size of 9 μm was obtained for both toners (comparedto 7 μm for Toner Formulation 1).

Triboelectric charge and development properties of Toner Formulations 2and 3 were determined. Triboelectric charge properties were measured asbefore for both toners at 4% TC on the standard silicone coated ferritecarrier.

Q/M=+27.1 μC/g  Pseudo toner Formulation 2:

Q/M=+29.1 μC/g  Pseudo toner Formulation 3:

Again it was noted that the toners charged very well and very fastagainst the carrier. No signs of toner dusting were observed, consistentwith these high values of triboelectric charge.

Comparison with Formulation 1 shows that the triboelectric chargingbehavior of Pseudo toner Formulations 2 and 3 are not significantlydifferent from each other or from Formulation 1 (Q/M=+35.7). Indeedthese slightly lower values could be attributed solely to the differencein mean particle size of formulations 2 and 3.

Conclusions

It would appear that the usual effects of increased negative CCA and theuse of a more negative carbon black have not overcome the intrinsicpositive charging due to the toner resins.

Formulations 2 and 3 were then surface treated with 2% fumed silica TG811F. The following results were obtained:

Formulation 2+2% Silica Q/M=−9.1 μC/g

Formulation 3+2% Silica Q/M=−9.0 μC/g

Again the desired value of −25 μC/g could not be obtained.

When roll milling these silica treated toners with the carrier,excessive toner dusting and clouding were noticed, indicating a lot oflow charge or wrong sign toner, and instability.

The performance of these toners in the Optra C cartridges was not at allsatisfactory. Excessive toner flow and very low charging levels(actually impossible to measure accurately) led to massive toner dumpingand very poor surface coverage of the toner on the Optra C developerroller. Unfortunately these problems would make it impossible to tryprinting the toner in the Optra C printer, owing to very unstableconditions.

It is believed that the Procote 200, or possibly something in the Soybased polyester, is acting as a very effective Positive charge controlagent. Formulating a toner without the ProCote 200 could prove this.

Section 2 Additional Toner Preparation Note: Toner 57 is Pseudo TonerFormulation 3 Black Toner 3

Carbon Black (Acidic type Raven 1255) 10.0 Experimental Soy dimer acidpolymer 78.5 Soy Protein Dupont ProCote 200 8.5 CCA Azo Spilon TRH 3.0TOTAL 100.0

Toners 58A and 58B are Pseudo Toner Formulation 2 Black Toner 2

Parts by weight Carbon Black (Acidic type Raven 1255) 10.0 ExperimentalSoy dimer acid polymer 70.00 Soy Protein Dupont ProCote 200 17.00 CCAAzo Spilon TRH 3.0 TOTAL 100.0

The differences in 58A and 58B are only minor variations in particlesize distribution.

The triboelectric charge of Toner 57 and Toner 58B were retested usinganother standard silicone coated Cu Zn ferrite that had been used as astandard test material. This is the carrier labeled FCX 5706. Thiscarrier is a little different in charging behavior to the siliconecoated ferrite carrier used before FCX 5557, but only slightly. It isslightly less negative charging than the previous carrier, but onlyslightly. The new carrier FCX 5706 was used simply because more of itwas available. It was noted that the silicone coated ferrite carriersare designed to charge toners negatively, not positively, but the soybased pseudo toners charge very positively against them.

Triboelectric Charging Results

Nominal Toner Concentration on carrier=4%Roll time=45 minutesTriboelectric charge measured in triplicate using standard Faraday cageBlow-off technique.Faraday cage with 400 mesh screen (retains all particles above 38microns)

Results are shown in Table 9 below.

TABLE 9 Q/M Q/M Against Carrier FCX Against Carrier FCX TONER 5557 570657 +29.1 μC/g +32.5 μC/g 58B +27.1 μC/g +37.3 μC/g

Recovery of toner in the blow-off experiments was acceptable, leadingcredence to the results. Typically between 3.5 and 3.7% toner was blownoff (cf. 4.0% originally on carrier). No significant dusting (tonerpowder clouding) was observed during rolling in the bottle, indicatingthat the toner was charging well against the carrier.

Typical copiers where a positively charged toner is useful include theXerox 10 series and Xerox 50 series light lens copiers; the Kodak (nowHeidelberg Digital) 2085 copier and similar products (3100) that all useKodak HX or IX toner. These products are all medium to high speedcopiers.

It was decided to compare the Kodak HX developer for chargingproperties. The Kodak two component development unit is called SPD(stands for small particle development subsystem). It uses a permanentlymagnetized small size (˜30 micron) Kynar coated Strontium ferritecarrier and employs a high working toner concentration of around 10%.The measured triboelectric charge of the HX toner in the HX developergave a Q/M value of +15 μC/gram. Because of the small size carrier thisQ/M measurement must be carried out on a special triboelectric chargemeasuring device called a MECCA device. A TC of 9.7% was obtained.

The HX toner at 10% TC was also measured against a similar kynar coatedstrontium ferrite carrier from PowderTech (FCX 6367) and obtained avalue of +35.6 μC/gram, and a recovered TC of 9.8%

Using this same PowderTech carrier (FCX 6367) and using 10% TC of TonerFormulation 57 a very highly positive charging system was obtained, Q/Mwas +112 μC/gram, and a recovered TC of 7.3% was obtained. This againindicates the very highly positive charging nature of the soy-basedtoners. However, with appropriate formulation and judicious choice oftoner surface additives and toner particle size, it appears possible toprepare a toner that would work in the Kodak copiers.

Section 3

It appears that the untreated toners 57 and 58 charged to a level ofabout +23 microCoulomb/g against the Toshiba carrier at 6% tonerconcentration. Also, these toners (57 and 58) charged to a level ofabout 23 microCoulomb/gram against the standard silicone coated ferritecarrier FCX 5706 at 3% toner concentration. This does not mean that thetwo different carriers have the same charging characteristics. They may,if there is no limiting number of charging sites on the carrier, i.e.there is no toner concentration dependence up to 6% toner concentration.However, there may be a toner concentration dependence if one or both ofthese carriers have a limited number of charging sites. In this case, itwould be expected to see the triboelectric charge on the toner dropsignificantly as the toner concentration increases.

It appears that the results at 6% toner concentration with the carrierFBF-300, one needs to adjust the triboelectric charge of toners 57 and58 downwards, from about +23 to around +13 microCoulomb/gram. Initially,the Cabosil TG 308F should be used to do this. Also 0.2% of the silicaon the toner should be performed initially.

The silica is then blended at the highest speed of the kitchen blenderfor 2 times 30 seconds. That is 30 seconds on, followed by 30 secondsoff, and followed by 30 seconds on. During the “off” stage lightly shakethe vessel to make sure that no toner has stagnated somewhere in thevessel.

When determining the amount of toner to use in the blending, the mixingvessel to should be filled to about 40% of its volume. The toner isplaced in the vessel first, followed by the fumed silica. When thevessel is filled to about 40% of its volume, this allows the necessary“vortex action” to occur when the blender is activated.

The triboelectric charge of the toner now treated with 0.2% silica isthen measured, and assessed whether the triboelectric charge has droppedto about +13 microCoulomb/g. If it has not, these steps are repeatedwith larger amounts of the silica, until the desired level of +13microCoulomb/g. has been achieved.

Section 4

Triboelectric charging properties of Toner No. 4 in the series of tonersusing the thermoplastic and protein based resins.

Toner formulation No. 4 has the following base formulation:

Black Toner No. 4

Parts by weight Carbon Black (Acidic Raven 1255) 10.0 Experimental Soydimer acid polymer 88.00 CCA Azo Spilon TRH 2.0 TOTAL 100.0 Notes: 1.there is no soy protein ProCote 200 in this formulation. 2. Raven 1255is a negative charging acidic carbon black. 3. Azo Spilon TRH is a blacknegative charge control agent.

The purpose of this formulation is to gain understanding of thefundamental charging characteristics of the soy dimer acid polymer. Itwas hypothesized that the high positive charging tendency of theprevious mixed polymer toners was primarily due to the inclusion of thesoy protein Pro-Cote 200 in the base formulations. Accordingly, this newformulation No. 4 was prepared in anticipation that it would not exhibitstrong positive charging characteristics. As can be seen below, this wasnot the case.

Toner formulation No. 4 had the following particle size characteristics.The toner was ground (air jet milling) very smoothly and efficiently,with no change in particle size median during grinding. Subsequentparticle size classification, also occurred efficiently, and a verynarrow particle size distribution around a volume median of 8.0 micronwas obtained.

D50=8.0 micron

D50/d10=1.28

D90/d50=1.25

Triboelectric Charging Properties

In the following table, there is shown the measured triboelectric chargeof the base (virgin) toner and toners prepared by blending severaldifferent levels of fumed silica onto the surface. The fumed silica usedwas one of the most inherently negative charging silicas supplied byCabot Corporation, Cabosil TG 811F. Additive blending was performed in aHamilton Beach 16 speed food blender (model No. 56200 at the highestspeed setting for 2 times 30 seconds blending, with a 30 second rest inbetween blendings.

The triboelectric charge was measured against a standard silicone coatedCopper Zinc ferrite carrier FCX 5706, supplied by PowderTech. Thiscarrier is very similar in its charging properties to a previously usedstandard silicone coated carrier FCX 5557. These Silicone coated ferritecarriers are designed to charge toner negatively.

Toner was roll milled in a glass jar against the carrier at 4% tonerconcentration (96 parts carrier to 4 parts toner; by weight) in eachcase for 45 minutes. Triboelectric charge was measured using thestandard blow off technique using a Faraday Cage manufactured by TorreyPines Research. Values are an average of three blow-off measurements.See Table 10 below.

TABLE 10 Triboelectric Toner Charge % Recovery Treatment μC/gram onblowoff Comments None (virgin +37.4 3.7% Rapid charging, no dusting,toner) small amount of free toner 0.3% TG811F +25.4 3.7% Good charging,no dusting 0.5% TG811F +14.5 4.0% Excellent charging, no dusting 1.0%TG811F +1.6 3.4% Significant dusting and free toner Consistent with thelow charge level 2.5% TG811F −10.8 3.15%  Significant dusting, and muchfree toner as indicated by the low recovery on blow-off. This isindicative of low charge toner and also probably some wrong sign toner.

It was noted that Toner No. 4 charged inherently to a high positivecharge. Addition of more and more of the negative silica resulted in aless positive toner. This is the expected result. It is also noted,however, that even with 1% silica the toner is still weakly positive. Itis not possible to blend more than about 2.5% silica onto toner of thissize without exceeding complete surface coverage. Although it ispossible to drive the toner negative with this large amount of silicaadditive, this is not a practical solution, since much toner dusting(toner not associated with carrier) was observed, and this will lead tosignificant problems in machine use. In addition, it was not possible todrive the toner to the desired negative value of −25 μC/gram againstthis particular carrier. This is the target value for use of the tonerin a typical Discharge Area Development system (DAD) used in modernprinters and digital copiers.

The value of +37.5 μC/gram observed for the untreated virgin toner No. 4(no surface additives) was very similar to the values obtained fortoners 2 and 3 (coded 57 and 58B), which contain both the dimer acidpolymer and the soy protein Pro-Cote 200. See Table 9 above

This indicated that it is not the protein Pro-Cote 200 which is theinherent positive charging material, but, in fact, the dimer acidpolymer appears to be the major driver for positive charge.

Even though it was not possible to achieve the target charge of −25 μC/gagainst the carrier, another evaluation of the toner in an OptraCcartridge was made.

Key functional parameters to achieve in the cartridge are the correctcharge and powder flow properties, as well as the metered loading oftoner on the aluminum development roller of the cartridge.

The toner should charge to Q/M=−10 to −12 μC/g and have a mass per unitarea of toner on the development roller M/A between 0.55 and 0.6 mg/cm².

The measured parameters were:

Q/M=−2 to −4 μC/g

M/A˜0.2 mg/cm²

In addition it was noted that the toner flowed too well (like water) andcaused excessive toner “dumping” and toner overflow from the cartridge.These symptoms are typically associated with insufficient triboelectriccharge on the toner, wrong sign toner, and inability of the meteringblade to constrain the toner, and toner powder flow properties that aretoo good. The low value of triboelectric charge may also indicateexcessive wrong sign toner or very low charge toner, as the Q/M value isan average charge of the toner

The dimer acid polymer appears to be the predominant driver towards thepositive triboelectric charging behavior of toners based on the twoSoy-based polymers.

It is not possible to overcome these highly positive chargingcharacteristics by the usual toner formulation methods, namely the useof internal negative charge control additives, and surface treatmentswith negative charging fumed silica. This infers that this particularresin system will not be useful for typical negative charging tonerdesigns (DAD systems), but is useful for positive toner designs, such asthose exemplified by the Kyocera type toners. On the other hand,selection of appropriate materials in preparation of the thermoplasticpolymers such as styrene and others known in the art can be used toreduce positive charges.

Section 5

This section illustrates triboelectric charge results on Toshiba TypeDeveloper (Toshiba Type Carrier and Toshiba type toner mixture. Thetriboelectric charge on the Toshiba type toner using the small sample ofdeveloper was measured. The sample was roll-milled for 10 minutes inorder to establish good charging, and then measured using the TPRblow-off triboelectric charge technique.

The sample was measured in triplicate and the results were in goodagreement and were averaged: q/M=+15.8 μCoulombs/gram. Blow-off recoveryof toner indicated a toner concentration on the carrier of 5.8%. Notoner dusting was observed, indicating uniform charging of the toner.

Samples of toners and developers were prepared as follows:

(a). Toner No. 4 750 grams (this is the toner based on the dimer acidpolyester only, with no Pro-cote 200 in the formulation.(b). 60 grams Toner No. 4 surface treated with 0.3% Cabosil fused silicaTG811F(c). 60 grams Toner No. 4 surface treated with 0.5% Cabosil fused silicaTG811F(d). 60 grams Toner No. 4 surface treated with 1.0% Cabosil fused silicaTG811F(e). 60 grams Toner No. 4 surface treated with 2.5% Cabosil fused silicaTG811F

The triboelectric charge results obtained with these toner samples (a)through (e) roll-milled at 4% TC against the standard silicone coatedCu—Zn ferrite FCX 5706 are listed below and Table 10.

(a). +37.4 μC/g (b). +25.4 μC/g (c). +14.5 μC/g (d). +1.6 μC/g (e).−10.8 μC/g

About 8 grams of each of the developers, containing these toners (a)through (e) were prepared.

It is suggested to shake or roll-mill the developers for a few minutesbefore measuring the blow-off triboelectric charge.

Using the 60 gram samples of surface treated toners, equilibration ofthese toners with the Toshiba carrier, at 6% Toner Concentration, for30-45 minutes and measurement of the triboelectric charge on the tonersshould give the same trend in charging as observed above.

It is preferred to take the precaution of breaking down these aggregatesby pre-grinding the silica (as received) in a small electric coffeegrinder, which can be obtained from a department store (such as a Brauncoffee grinder from Sears etc).

It appears that the dimer acid polymer derived from soya beans is themain material responsible for directing the toners to an extremely highpositive charge. The material appears useful in magnetic SCD type tonersthat will function in Kyocera Ecosys type printer cartridges. These typeof toners are required to charge quite positively.

Section 6

The Kyocera toners are exemplary of positively charging toners used inDAD printers, since they employ the amorphous silicon photoreceptor,which is a positively charged photoreceptor drum, in contrast to themuch more common negatively charged “Organic photoconductor” or “OPC”drums used in most other printers and copiers, and which use negativelycharged toners.

The Kyocera toners are also magnetic single component developmenttoners, appearing to employ about 40% black magnetite as the colorant.

Toner Formulation

The following base toner formulation was prepared:

Ingredient % by weight Toda magnetite 40 Shamrock Wax PP CP40 6 Totalresin mixture 54 Charge Control Agent NONE Note 1: The resin mixtureconsists of the resins prepared as disclosed herein at a ratio 95 partsby weight of the dimer acid polymer to 5 parts by weight of the soyisolate protein, this gives a protein content of approximately 3% in thetoner. Note 2: No positive charge control additive was used in thisexperimental toner, based mainly on the fact that very high positivecharging of previous carbon black experimental toners based on thepolyamide resins had been observed.

The amount of wax from 3% used in a Kyocera type toner to 6% in thisexperimental toner, due to the propensity for Hot Offset, that might beobserved due to the very low melt behavior that was observed for theresin mixture in Shimadzu flow test experiments carried out 180° C. (theapproximate set point fuser roll temperature of a Kyocera printer). Itwas expected that the increased amount of wax would to some extentincrease the fusing latitude of the experimental toner. However, as willbe mentioned later, significant Hot Offset was observed during printruns with the experimental toner.

The formulation outlined above was melt blended with no problems. Thematerial was then jetted and classified with no problems and in goodyield with very good control of the targeted particle size and theparticle size distribution. The volume mean particle size of theexperimental soy based toner was 7.3 microns

The volume mean particle size of the standard Kyocera toner was 7.9microns.

The targeted triboelectric charge for the Kyocera type toner isq/M=+13-+14 μC/g against a standard carrier. A positive charge controlagent can be incorporated into the base toner, to give a positive charge(e.g. of about +20 μC/g), then by using negative directing surfaceadditives to bring the charge down.

The triboelectric charge of the base experimental toner was measured as+9 μC/g, and this was raised slightly to +11 μC/g through the use of apositive directing silica. The silica was needed to significantlyimprove the powder flow properties of the toner in order that printtests could be performed.

NOTE: With hindsight, it appears that it would have been better toincorporate some positive charge control agent in the experimental tonerin order to obtain a more positive charge.

Both the experimental Soy based toner (with surface additives) and theKyocera type toner (with surface additives) were used to run 500 printtests, in order to collect sufficient prints for a paperrepulping/recycling test. The results of the print tests were notentirely satisfactory. The Kyocera type toner produced high imagedensity prints with no background and no fading of image density onrunning 500 consecutive prints. The polyamide resin-based toner printedwith fair density initially, but faded considerably over 500 prints. Itappears this is because the triboelectric charge level and powder flowproperties were not exactly meeting the printer specifications. Inaddition, as anticipated the polyamide resin-based toner exhibitedsevere Hot Offsetting properties due to the low melt/narrow fusinglatitude behavior of the toner. However 500 prints from each toner wereprepared.

It appears that by appropriately tuning the molecular weightdistribution of the resins; the problems with fusing latitude can bealleviated. The problem was particularly severe here because of therelatively high set point temperature in the particular Kyocera printerused.

While the forms of the invention herein disclosed constitute presentlypreferred embodiments, many others are possible. It is not intendedherein to mention all of the possible equivalent forms or ramificationsof the invention. It is to be understood that the terms used herein aremerely descriptive, rather than limiting, and that various changes maybe made without departing from the spirit of the scope of the invention.

1-28. (canceled)
 29. A polyamide comprising the reaction product of: a.a dimer acid; b. a diamine; c. a protein derivative; and d. an aliphaticacid.
 30. (canceled)
 31. (canceled)
 32. (canceled)
 33. The polyamide ofclaim 29, wherein the aliphatic acid comprises adipic acid.
 34. Thepolyamide of claim 29, wherein the protein derivative is a dibasic aminoacid.
 35. The polyamide of claim 29, wherein the dimer acid comprisesone or more dimers of C18 unsaturated fatty acids.
 36. The polyamide ofclaim 29, wherein the dimer acid comprises one or more dimer acidsselected from:


37. The polyamide of claim 29, wherein the dimer acid is a soy-baseddimer acid.
 38. The polyamide of claim 29, wherein the dimer acidcomprises formula 1:


39. The polyamide of claim 29, wherein the diamine is a rigid diamine.40. The polyamide of claim 29, wherein the diamine isbis(4-aminocyclohexyl)methane.
 41. The polyamide of claim 34, whereinthe dibasic amino acid is selected from the group consisting of glutamicacid, aspartic acid, and mixtures thereof.
 42. The polyamide of claim29, wherein the polyamide comprises a polystyrene acrylate.
 43. Thepolyamide of claim 29, wherein the polyamide comprises a polyester. 44.The polyamide of claim 29, wherein the polyamide comprises a polyesterether.
 45. The polyamide of claim 29, wherein the polyamide comprises apolyurethane.